Resinous polymer of methylene dioxolane



Patented Aug. 14, 1945 RESINOUS POLYMER OF METHYLENE DIOXOLANE William 0. Kenyon and Thomas F. Murray, Jr., Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. 1, a corporation of New Jersey No Drawing. Application September 8, 1943, Serial No. 501,548

8 Claims. (Cl. 260-80) This invention relates to resinous polymersand more particularly to copolymers obtained by the conjoint polymerization of 4-methylene-L3-dioxolanes with other unsaturated organic compounds. This application is a continuation-inpart of our copending application Serial No. 454,- 906, filed August 15, 1942.

Monomeric 4-methylene-1,3-dioxolanes having the following general formula:

wherein R and R each represents hydrogen, an alkyl group or an aryl group can be prepared by the method of H. O. L. Fischer et al., Ber. 63 B, 1732 to 1744 (1930). Attempts to homopolymerise such monomers wherein R represents hydrogen and R represents an alkyl group .have

failed.

We have now found that 4-methylene1,3-dioxolanes can be copolymerized with other unsaturated organic compounds to yield useful resinous materials. Moreover, we have found that 4-methylene-2-phenyl-1,3-di0xo1anes, as well as other z-aryl-i-methylene-1,3-dioxolanes can be homopolymerlzed. It is, accordingly, an object of our invention to provide new resinous polymers and to provide a process for preparing the same. Other objects will become apparent hereinafter.

In accordance with our invention, we copolymerize a 4-methylene-1,3-dioxolane with an unsaturated organic compound, especially an unsaturated organic compound containing a carbonto-carbon double bond conjugated with a carbonto-oxygen double bond, such as a-methylene carboxylic acids and their esters, vinyl ketones and anhydrides of ethylene-1,2-carboxylic acids. With many of such unsaturated organic compounds, the 4-methylenc-l,3-dioxolanes copolymerize very the polymerization is advantageously accelerated by heating or by the use of catalysts, such as the catalysts which are known to effect the polymerization of organic compounds containing a group, e. g. organic peroxides such as benzoyl peroxide, acetyl benzoyl peroxide, etc;

The following examples will serve to illustrate our new resinous polymers and the process for preparing the same.

Example 1.-Copolymer of 2-methyl-4-methylene-1,3-di0:colane and a-methacrylic acid 5 g. of 2-methyl-4-methylene-1,3-dioxolane and 5 g. of a-methacrylic acid were mixed. The mixture warmed spontaneously and became hard. The hard product was brilliant, clear and colorless. It was dissolved in a mixture of acetone and water and precipitated by pouring the solution into a mixture of two volumes acetone and one volume of diethyl ether. The product was fioccuv lent when precipitated but became sticky when brought from the precipitating liquid into the air. It was dried at 60 C., giving a brittle, glossy, colorless material. The material was analyzed for carbon and hydrogen and found to contain 54.66 per cent by weight of carbon and 7.69 per cent of hydrogen. A similar product was dissolved in water and titrated with standard sodium hydroxide. It was found to contain 66.5 per cent of a-methacrylic acid. From these results it appeared that some acetaldehyde was split off from the dioxolane during polymerization, and that the copolymer contained a-methacrylic acid 66.5 per cent, dioxolane compound 11.4 per cent and the corresponding dialcohol 22.1 per cent.

Varying the proportion of the monomers used affects the type of copolymer obtained with a-methacrylic acid. Below are given the results Example 2.-Copolymer of 2-methyl-4-methylene -1,3-di0a:olane and maleic anhydride When 2-methyl-4-methylene-1,3-dioxolane and maleic anhydride were mixed, they reacted violently, giving of! considerable heat and producing a dark polymer. Thereaction can be modified by carrying it out in a diluent, such as acetone or preferably 1,4-dioxane.

25 g. of maleic anhydride were dissolved in g. of dry 1,4-dioxane. 25 g. of 2-methyl-5i-methylene-l,3-dioxolane were added to the solution.

Reaction began with external heating and was modified by slight warming or cooling, as required, by running water over the flask in which the reaction was being carried out. When the reaction mixture has become quite viscous, 1t

' was warmed on a steam bath for V2 hour. At

the end of this time, the reaction mixture was very viscous, clear and substantially colorless. It was diluted with 1,4-dioxane and the resinous copolymer was precipitated by pouring the dioxane mixture into benzene. The precipitated copolymer was dried at 50 to 60 C. and found to contain 53.43 per cent of carbon and per cent of hydrogen. These values agree well with the calculated values of 54.5 per cent of carbon and 5.06 per cent of hydrogen in a copolymer containing equimolecular proportions of maleic anhydride and the dioxolane.

Example 3.Cop0lymer of 2-methyl-4-methylene-1,3-dioxolane and methyl a-methacrylate A mixture was made of 4 g. of 2-methyl-4- methylene-1,3-dioxolane, 16 g, of methyl a-methacrylate and 0.2 g. of benzoyl peroxide. The vessel containing the mixture was closed and maintained at 60 C. for 24 hours. A hard clear, colorless copolymer resulted. The copolymer was dissolved in acetone and precipitated by pouring the acetone solution into water. Although the dioxolane in the starting reaction mixture was equal to 20 per cent by weight of reaction mixture, the copolymer contained only 6.05 per cent combineddioxolane. When per cent of the dioxolane was employed in the starting reaction mixture, the copolymer contained 4.6 per cent and when 40 per cent of the dioxolane was employed in the starting reaction mixture, the co-' polymer contained 11.25 per cent combined dioxolane.

A series of these copolymers of 2-methyl-4- methylene-1,3-dioxolane and methyl a-methacrylate were compression molded and the physical properties of the molded products compared.

Ratio of dioxolane to methyl a-methacrylateinstartingreactionmixture 10/90 /85 20180 30/70 Impactstrength 9.16 4.64 3.90 2.69 Hardness:

Shore 83.8 86.0 84.0 64.8

Rockwell 107.6 100.4 91.6 27.6 Elongation, percent 4.33 4.00 7.66 3.66 Strength:

Tensile 7,100 4,820 6,060 1,440

Flexural .l4,920 8,180 9,590 1,016

Example 4.-Copolymer of Z-methyl-d-methylene-1,3-diox0lane and acrylic acid 10 g. of acrylic acid were dissolved in g. of dry 1,4-dioxane. To the solution were added 10 g. of 2-methyl-4-methylene-1,3-dioxolane. The mixture was heated in a 60 C. bath under a reflux condenser. In about /2 hour the reaction mixture had become a viscous solution. Heating was continued for about 3 additional hours: The reaction mixture was then diluted with 1,4-dioxane and the copolymer precipitated by pouring the di'oxane solution into carbon tetrachloride.

Example 5.-C'opolymer of 2-methyl-4-methylens-1.3-diozolane and methyl acrylate A mixture was made of 25 g. or 2-methyl-4- methylene-1,3-dioxolane, 25 g. of methyl acrylate and 0.5 g. of benzoyl peroxide. The mixture was warmed under reflux at 60 C. for about 6 hours and then cooled. Polymerization was very smooth. The resulting polymer was very soft and tacky.

Example 6.-Copolymer'of 2-meihyl-4-methylene-1,3-dioa:olane and methyl vinyl ketone A mixture or equal parts of 2-methyl-4-methylene-1,3-dioxolane and methyl vinyl ketone gave a soft polymer in about 72 hours, warming at 60 C. with no catalyst.

Example 7.C'opolymer of 2-methyZ-4-methylene-1,3-dio:colane, vinyl acetate and a-meihacrylic acid A solid, though soft, copolymer was obtained when a mixture of 5 g. of 2-methyl-4-methylene- 1,3-dioxolane, 5 g. of vinyl acetate and 1 g. of methacrylic acid were kept at 60 C. for 24 hours. No catalyst was used.

Ezample 8.Copolymer of 4-methylene-1,3-diozolane and a-methacrylic acid 5 g. of 4-methylene-Lil-dioxolane and 5 g. of methacrylic acid were mixed. After one hour standing at 20 to 25 C., no significant polymerization had occurred. The 'mixture was then placed in an oven at 60 C. and allowed to stand at this temperature 12 to 15 hours. A solid, hard, clear, bubble-free resinous copolymers was ob tained.

Example 9.Copolymer of 4-methylene-1,3-dioaolane and methyl a-methacrylate 37.5 g. of 4-methylene-1,3-dioxolane and 87.5 g. of methyl a-methacrylate and 1.0 g. of benzoyl peroxide were mixed and the mixture heated in a hot water bath at 40 C. After 48 hours a hard, clear, colorless resinous copolymer was obtained. The copolymer did not retain its shape well upon molding.

Example 11.Copolymer of 2-phenyl-4-methylene-1,3-dio:z:olane and ll-methacrylic acid 8 g. of z-phenyl-i-methylene1,3-dioxolane and 4.3 g. of a-methacrylic acid were mixed. Polymerization occurred spontaneously at 20 to 25 C. in a few minutes to give a slightly cloudy, slightly soft resinous copolymer which became hard in about 72 hours.. The copolymer was soluble in acetone but practically insoluble in 10 per cent aqueous sodium hydroxide, although it swelled some in this reagent and turned reddish brown.

Example 12.--Copolumer o/ 2,2-dlmethul-4-methplane-1,3-dloxolane and maleic anhz dride Equimolecular proportions of -2,2-dimethyl-4- methylene-1,3-dioxolane and maleic anhydride reacted so vigorously that it was necessary to cool the mixture to control the polymerization. At the end of one hour at 20 to 25 C., the polymerization product was too viscous to flow and upon further standing at 20 to 25 C. an opaque resinous copolymer obtained.

Example 13.-Copolymer of zephenylt-methylene-LZi-clioxolane and maleic anhudride Equimolecular proportions of 2-phenyl-4- methylene-1,3-dioxolane and maleic anhydride reacted vigorously as in the preceding Example 12 with similar results.

Example 14.C'opolymer of Z methu'lene-IA- dioa'aspirolifilaecane and a-methacrylic acid Example 15.-Copolymer of 2-metlwlene-L4- diozaspiro[4.5ldecane and methyl a-fllflthdOflllate 7.8 g. of Z-methylene-1,4-dioxaspiro[4.5ldecane were mixed with g. of methyl a-methacrylate. 0.13 g. or benzoyl peroxide were added to the mixture. The resulting mixture was heated at 50 to 80 C. for 24 hours. A soft copolymer resulted which was dissolved in acetone. The acetone solution was poured into water to precipitate the copolymer which was dried. at 50 to 60 C. Analysis showed a carbon content of 64.4 per cent and a hydrogen content of 8.3 per cent. This carbon content indicated that the copolymer contained 58 per cent of combined methyl methacrylate. Two methoxyl determinations showed an average value 01 16 per cent for methoxyl 54 per cent combined methyl a-methacrylate.

ture rose spontaneously, and in a few minutes the mixture was too viscous to flow. It was allowed to stand at 20 to C. for 72 hours. whereupon a hard, clear, colorless copolymer was obtained. This was dissolved in acetone. The acetone solution was poured into diethyl ether to precipitate the copolymer. The copolymer was washed with diethyl ether, and dried in vacuo at 20 to 25 C. The copolymer contained 67.86 per cent or carbon and 6.72 per cent of hydrogen which compared reasonably well with the calculated values of carbon 68.8 per cent and hydrogen 6.88 per cent for a copolymer containing equimolecular proportions oi combined dioxolane and a-methacrylic acid.

Example 18.Copolymer of Z-(p-chlorophenyl) 4-methylene-1,3-diozc0lane and a-methacryllc acid 8.8 g. of 2-(p- -chlorophenyl)-4-methylene-1,3- dioxolane and 4.3 g. of methacrylic acid were mixed and the mixture heated in an oven at 50 I to 60 C. At the end of four days, a clear, hard,

oaaspir0[4.5ldecane and maleic anhz/dride 7.8 g. of 2-methylene-1,4-dioxaspiro[4.5]decane were mixed with 5 g. 01 maleic anhydride. The mixture polymerized spontaneously and produced a yellowish brown polymer. This was dissolved in acetone. The copolymer was precipitated by pouring the acetone solution into diethyl ether. The resin was filtered off, washed with diethyl ether and dried. The two monomers were employed in equimolecular proportion, and if combined in equimolecular roportion, the calculated carbon and hydrogen contents of the copolymers would be 61.9 per cent and 6.34 per cent respectively. The analytical values obtained were 61.4 per cent of carbon and 6.24 per cent of hydrogen.

Example 17.C'opol:umer of Z-(m-tolrl) -4- methylene-1,3-dloxolane and a-methacrulic acid 8.8 g. of Z-(m-tolyl)-4-methylene 1,3-dioxolane and 4.3 g. (an equimolecular proportion) of a-methacrylic acid were mixed. The temperacolorless copolymer had formed.

Example 19.C0pol1'/mer of 2-methp1l-4-methylene-1,3-dioaolane and methyl lsopropem/l ketone 5 g. of 2-methyl-4-methylene-1,3-dioxolane were mixed with 5 g. 01' methyl isopropenyl ketone. The mixture was allowed to stand at 20 to 25 C. for 72 hours with no apparent change.

0.1 g. of benzoyl peroxide catalyst was added to 72 per cent or the copolymer was combined iso-' propenyl ketone and the remainder combined dioxolane.

Example 20.--Homopolymer methylene-1,3-dloxolane 10 g. of 2-phenyl-4-methylene-1,3-dioxolane were mixed with 0.1 g. of benzoyl peroxide. The mixture was heated at to C. for 48 hours. The homopolymer which formed was hard and clear. It was soluble in acetone and precipitated when the acetone solution was poured into water.

Example 21.--Homopolymer of 2,2-dimethyl-4- methylene-1,3-dioa'olane Example 22.-Copolvmerisation of Z-methylene- 1.4-dloxaspiro[4.5ldecane with a-methacrylic acid 5 g. of Z-methylene-1,4-dioxaspiro [4.5ldecane prepared by dehydrohalogenating the cyclohexanone ketal ol glycerol a-monochlorohydrin (2- of 2-phenyl-4- resinous polymers can also be successfully applied to the manufacture of laminated sheets of materials such as glass, cellulose nitrate, cellulose acetate, or wood. The polymers can also be used to impregnate fabrics, wood and the like, for the purpose of water-proofing and preservation. Our resinous polymers can also be extruded into the form of film or sheet. Film or sheet can also be made from the polymers by dissolving about one part of the polymer in a suitable organic solvent which may be a single solvent or a mixture of solvents, and coating the resulting solution to desired thinness on a film-forming surface such as a glass or metal plate or .table or revolving drum. When the solvent has been evaporated (this can be conveniently accelerated by means of warm air), the resulting film or sheet can be stripped from the film-forming surface and subjected to curing (removal of excess solvent) by heating in warm air. The resulting cured film or sheet can be used for a variety of purposes including that of a support for light-sensitive photographic silver halide emulsions of the gelatino or other types. Plasticizers can be incorporated in the polymers prior to molding.

While the preparation of 4-methylene-L3-dioxolanes is described by H. O. L. Fischer et 'al. (supra), the following examples will serve to illustrate the preparation of some embodiments not specifically disclosed.

4- 2,382,640 methyl-Lorna methyl-1,3-dioxolan'e) in the Example 24.--2-methvlene-1,4-di0xaspiro[4.5lpresence of triethanol amine, were mixed with an decane equal weight or a-methacrylic acid. -Three days later, the mixture was thin and yellow. Upon g- 2c=c11, shaking, it became more viscous, and after a few 5 B208 05 hours standing, the viscosity had further in- \(7: (63/ 4 H creased. After an additional period ofd three H H, days hard yellow copolymer had forme 110 g of glycerol cr-Il'lOIiOChlOI'OhYdI'ill 110 g of nomon of the same dloxolane prepared as 10 cyclohexane and 10 cc. of concentrated hydroindicated above was extracted with 10 per cent chlonc acid (about 36 per cent hydrogen ch10- aqueous acetic acid The aqueous and layer beride) were heated on a. steam bath for one hour. came light brown in color and t e layer 01 At, the end of this time ice was added to the mixi was com-less The dloxolane layer was ture and the lower layer was separated oil and dried over magnesium sulfate and potassium washed with water at about 23 C. To the washed carbonate, filtered from these salts and distilled. product were added 15 g of triethanol amine, and The dmxolane treatedm flitshmanner fl x g the resulting mixture was heated in an oil bath promptly wmn mixed W1 an equa 0 at 145 C. under a refluxed condenser. 40 g. of a-methacryhc acid powdered sodium hydroxide were added to the reaction mixture through the condenser. The f i'figgfiz ig 3 232 2 5 ethyl resulting mixture was heated at 145 C. for two hours, following which the volatile products were 1 of 2.. t 1-4- t 1 1 3 1 19 distilled oil under reduced pressure. The disof acrylo nit fl and 02 of benzoyl peroxide tillate was washed with 10 per cent aqueous acetic were mixed together and heated at 50 to 60 C. acid, r l fi with distilled W ter, attil ffinallyhdrled t 1 ,11; O 1 resultei over a ydric potassium carbona or 24 ours. g-fi i lg g ix 3p is-, gi 0 fo 20 The carbonate was removed by filtration and they minutes in order to remove monomers. At the f dlstllled under reduced pressulfe using 8 end of this time, the copolymer possessed no odor modlfied 01818611 a of monomers. A sample of the copolymer was Example 25 2-phenyl-4-methylene-1,3- analyzed and found to contain 66.54 per cent of dioxolane carbon, 6.45 per cent of hydrogen and 20.12 per 0 H O C CH cent of nitrogen. This analysis indicated that /3 4 the copolymer contained six acrylo nitrile groups c2\- 6 for each dioxolanelgroup. 11 m1 f n o-oH,

Our resinous po ymers are especia y use or the manufacture of molding articles. The moldg fifi g g gg ggg z gggggi gg gg 32 3 ing can be accomplished by causing the polymers Claisen flask The mixture was heaked for to form in a suitable mold or by compressing the three hours at 6 C (:50) during which time polymers after the-y have formed by means 40 a small amount of water distilled. The mixture of the usual mommg machmery' Those-Of w was then distilled under reduced pressure, wherepolymers which show satisfactory solubility 1n upon a foremn of benzaldehyde resulted e organic solvents can be made up into varnishes benzal bmonocmomhydrm boned at 120 6 or lacquers with or without the addition of other C at 6 mm of Hg ressure the large j ty resinous bodies or cellulose derivatives. The distilling at'about 5 0 he benzal nochlorohydrin was placed in a flask with 150 g. of crushed potassium hydride and heated at C. for hour and the temperature was then raised to C. to C. for a further 1% hours. After cooling, the excess potassium hydride and the potassium chloride were dissolved in 500 cc. of water and the resulting oil was taken up with diethyl ether. After drying the ether solution over potassium carbonate, the ether was evaporated and the residue distilled under reduced pressure using a modified Claisen flask. The dioxolane compound boiled at 87 to 89 C. at 3 mm. 0! 8 pressure.

Example 26.-4-methylene-1,3-di0xolane 120 g. of trioxymethylene, 450 g. of glycerol amono-chlorohydrin and 50 :cc. of concentrated hydrochloric acid (about 36 per cent hydrogen chloride) were mixed together and heated on a steam bath under a refluxed condenser for one hour. The clear liquid thus dbtained was washed with water and mixed with 30 cc. of triethanol amine and 120 g. of powdered sodium hydroxide. The mixture was heated in an oil bath, at refluxing temperature, for 2 /2 hours. The resulting product was distilled through a short column.

Some water distilled over with the ll-methylene- 1,3-dioxolane. Water was separated OE and. the dioxolane washed with distilled water, and then dried over potassium carbonateJ, The dioxolane was redistilled through a col packed with copper helices. The boiling point was 87.5 C.

The dioxolane described in Example 24 and utilized in Examples 15, 16 and 22 is e. spiro compound since it contains one and only one carbon atom common to two ring systems and hence cannot be conveniently named in the same manner as the other dioxolanes. However, since the spiro compound is clearly a dioxolane of the same category as the other 4-methylene-1,3-dioxolanes, it is intended to come under the generic term "a 4-methylene-1,3-dioxolane. I

What We claim as our invention and desire to be secured by Letters, Patent of the United States is:

l. A resinous homopolymer of a 2-aryl-4- methylene-1,3-dioxolane.

2. A resinous homopolymer of a. 2-phenyl-4- methy1-1,3-diox0lane.

3. A resinous homopolymer of a 2-aryl-4- methylene-1,3-dioxolane in which the aryl group is a monocyclic aryl group of the benzene series.

4. A process for preparing a resinous homopolymer comprising polymerizing a 2-aryl-4- methylene-1,3-dioxolane.

5. A process for preparing a resinous homopolymer comprising polymerizing, in the presence of an organic peroxide polymerization catalyst, a 2-aryl-4-methylene-1,3-dioxolane.

6. A process for preparing a resinous homopolymer comprising polymerizing, in [the presence of a benzoyl peroxide polymerization catalyst, a 2-aryl-4-methylene-1J3-dioxolane.

'7. A process for preparing a. resinous homopolymer comprising polymerizing, in the presence of a. benzoyl' peroxide polymerization catalyst, a 2-aryl-4-methylene-1,3-diox0lane in which the aryl group is a monocyclic aryl group of the henzene series. 1

8. A process for preparing a resinou homopolymer comprising polymerizing, in the presence of a benzoyl peroxide poLvmerization catalyst, a. 2- phenyl-4-methylene-1,3-dioxolane.

WILLIAM O. KENYON. THOMAS F. MURRAY, JR. 

